CN114084877B - Method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece material and obtained ultrapure ferric phosphate - Google Patents
Method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece material and obtained ultrapure ferric phosphate Download PDFInfo
- Publication number
- CN114084877B CN114084877B CN202111252423.9A CN202111252423A CN114084877B CN 114084877 B CN114084877 B CN 114084877B CN 202111252423 A CN202111252423 A CN 202111252423A CN 114084877 B CN114084877 B CN 114084877B
- Authority
- CN
- China
- Prior art keywords
- lithium iron
- iron phosphate
- electrolyte
- pole piece
- waste lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 145
- 239000002699 waste material Substances 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 94
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 69
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 68
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 68
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 106
- 239000011149 active material Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 64
- 238000003860 storage Methods 0.000 claims description 42
- 239000012528 membrane Substances 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000013543 active substance Substances 0.000 claims description 24
- 239000003115 supporting electrolyte Substances 0.000 claims description 24
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 22
- -1 10-methylbenzoxazine Chemical compound 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 claims description 9
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical class CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 150000004897 thiazines Chemical class 0.000 claims description 6
- 150000007979 thiazole derivatives Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- XXENPMSFACKOFO-UHFFFAOYSA-N 1-(10h-phenothiazin-1-yl)ethanone Chemical compound S1C2=CC=CC=C2NC2=C1C=CC=C2C(=O)C XXENPMSFACKOFO-UHFFFAOYSA-N 0.000 claims description 3
- TUZVTRCMDIUEBE-UHFFFAOYSA-N 1-chloro-10h-phenothiazine Chemical compound S1C2=CC=CC=C2NC2=C1C=CC=C2Cl TUZVTRCMDIUEBE-UHFFFAOYSA-N 0.000 claims description 3
- ADIKQLIPZCZVJA-UHFFFAOYSA-N 5-chlorocyclopenta-1,3-diene;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.ClC1=CC=C[CH-]1 ADIKQLIPZCZVJA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- WQUBSYCLJSPOKV-UHFFFAOYSA-N 3h-1,2,3,5-dithiadiazole Chemical compound N1SSN=C1 WQUBSYCLJSPOKV-UHFFFAOYSA-N 0.000 claims description 2
- IZZXLRJWQXIKKC-UHFFFAOYSA-N 4-(4-methylphenyl)-3H-1,2,3,5-dithiadiazole Chemical compound Cc1ccc(cc1)C1=NSSN1 IZZXLRJWQXIKKC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 2
- HOBCNIBGJMNRAW-UHFFFAOYSA-N 4-phenyl-3H-1,2,3,5-dithiadiazole Chemical compound C1(=CC=CC=C1)C=1NSSN=1 HOBCNIBGJMNRAW-UHFFFAOYSA-N 0.000 claims description 2
- RWFIPXDWCJFXFM-UHFFFAOYSA-N 5-methyl-2-phenyl-1,3,2-benzodithiazole Chemical class S1C2=CC(C)=CC=C2SN1C1=CC=CC=C1 RWFIPXDWCJFXFM-UHFFFAOYSA-N 0.000 claims description 2
- JZFICWYCTCCINF-UHFFFAOYSA-N Thiadiazin Chemical compound S=C1SC(C)NC(C)N1CCN1C(=S)SC(C)NC1C JZFICWYCTCCINF-UHFFFAOYSA-N 0.000 claims description 2
- RKNFJIIYAUSTJA-UHFFFAOYSA-N bis(sulfanylidene)platinum Chemical compound S=[Pt]=S RKNFJIIYAUSTJA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 229910052722 tritium Inorganic materials 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims 1
- UKIQHUKAVQCABU-UHFFFAOYSA-N 3-(4-methoxyphenyl)-5,6-dimethyl-1,4,2-dithiazine Chemical compound C1=CC(OC)=CC=C1C1=NSC(C)=C(C)S1 UKIQHUKAVQCABU-UHFFFAOYSA-N 0.000 claims 1
- BQXBURSEUYMOFA-UHFFFAOYSA-N 5,6-dimethyl-3-phenyl-1,4,2-dithiazine Chemical compound S1C(C)=C(C)SC(C=2C=CC=CC=2)=N1 BQXBURSEUYMOFA-UHFFFAOYSA-N 0.000 claims 1
- OVUYEFLHMIBQIP-UHFFFAOYSA-N benzo[g][2,1,3]benzothiadiazole Chemical compound C1=CC2=CC=CC=C2C2=NSN=C21 OVUYEFLHMIBQIP-UHFFFAOYSA-N 0.000 claims 1
- 150000004870 dithiazoles Chemical class 0.000 claims 1
- 150000003216 pyrazines Chemical class 0.000 claims 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 16
- 238000004064 recycling Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 230000005611 electricity Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PEZNEXFPRSOYPL-UHFFFAOYSA-N (bis(trifluoroacetoxy)iodo)benzene Chemical compound FC(F)(F)C(=O)OI(OC(=O)C(F)(F)F)C1=CC=CC=C1 PEZNEXFPRSOYPL-UHFFFAOYSA-N 0.000 description 2
- ANUJXWUVZHMJDL-UHFFFAOYSA-N 1-bromocyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].BrC1=CC=C[CH-]1.BrC1=CC=C[CH-]1 ANUJXWUVZHMJDL-UHFFFAOYSA-N 0.000 description 2
- DGYYJSHANXEPSK-UHFFFAOYSA-N 1-methyl-10h-phenothiazine Chemical compound S1C2=CC=CC=C2NC2=C1C=CC=C2C DGYYJSHANXEPSK-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- LJBTWTBUIINKRU-UHFFFAOYSA-K cerium(3+);triperchlorate Chemical compound [Ce+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LJBTWTBUIINKRU-UHFFFAOYSA-K 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000264 sodium ferrocyanide Substances 0.000 description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- UDBAOKKMUMKEGZ-UHFFFAOYSA-K trichloromanganese Chemical compound [Cl-].[Cl-].[Cl-].[Mn+3] UDBAOKKMUMKEGZ-UHFFFAOYSA-K 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 229940041260 vanadyl sulfate Drugs 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- JKIAGXJEDAQJIN-UHFFFAOYSA-N CN(C=1NSSN=1)C Chemical compound CN(C=1NSSN=1)C JKIAGXJEDAQJIN-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 1
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- WWHCYTPHGOJLSN-UHFFFAOYSA-N tetraphenyl-$l^{5}-arsane Chemical compound C1=CC=CC=C1[AsH](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WWHCYTPHGOJLSN-UHFFFAOYSA-N 0.000 description 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials and the obtained ultrapure ferric phosphate, and the pretreated waste lithium iron phosphate pole piece materials are filled into a mesh bag; constructing a flow battery, wherein an oxidation-reduction pair with the potential higher than or equal to that of lithium iron phosphate is adopted as an active material in positive electrolyte; and taking out the waste lithium iron phosphate pole piece material after undergoing a charge-discharge cycle, and washing and drying to obtain the ultrapure ferric phosphate. The method for obtaining the ultrapure ferric phosphate from the waste lithium iron phosphate pole piece material and the obtained ultrapure ferric phosphate can realize recycling and sustainable recovery of the waste lithium iron phosphate, is beneficial to large-scale production and commercial production of a process for preparing the ultrapure ferric phosphate from the waste lithium iron phosphate by a propulsion flow battery, is expected to solve the problem of mass retirement of the waste lithium iron phosphate battery in the future, and completely realizes recycling of the waste lithium iron phosphate and preparation of the ultrapure ferric phosphate.
Description
Technical Field
The invention belongs to the technical field of preparing an ultrapure ferric phosphate precursor of lithium iron phosphate by recycling lithium iron phosphate, and relates to a method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials and the obtained ultrapure ferric phosphate.
Background
As one of the important development industries of new energy, the lithium ion battery is widely applied to the fields of new energy electric automobiles, solar illumination, aerospace, electric tools and the like, and the annual energy is huge, so that the huge scrapping problem of the lithium ion battery is brought along. If the components of the lithium ion battery including the anode material, the cathode material and the diaphragm material are directly abandoned, huge pressure is generated on the ecological environment, and huge economic burden is generated on production enterprises and application enterprises, so that the method has great environmental protection significance and economic significance for solving the resource recycling of the waste lithium ion battery.
The lithium iron phosphate pole piece material has the characteristics of large discharge capacity, long cycle life and the like, is a lithium ion battery pole piece material with excellent performance, and has great significance in resource recycling. At present, the recovery technology of waste lithium iron phosphate mainly uses chemical leaching, and has the key problems of large chemical consumption, serious secondary pollution, complicated procedure, high cost, small recovery benefit and the like, so that the regular recovery enterprise has high standard investment and environmental protection investment, and the situation that the enterprise is forced to purchase retired lithium ion power batteries at low price even in a gratuitous way, and the recovery and collection of the power batteries are difficult is caused. Meanwhile, compared with the waste ternary batteries, the waste lithium iron phosphate pole piece material recovery product has lower economic value, the prior art can only extract lithium elements in the lithium iron phosphate pole piece material, the lithium carbonate can be prepared by using the waste lithium iron phosphate pole piece material recovery product, and other elements such as iron elements, phosphorus elements and the like are only sold as waste residues to the cement building material industry, so that the recovery economic value is lower.
The purchasing cost of raw material iron phosphate of the existing lithium iron phosphate pole piece material is continuously increased, enterprises are hard to purchase, the yield of the lithium iron phosphate pole piece material is limited, a heavy cost burden is caused for the production enterprises, and the current production situation of the existing lithium iron phosphate pole piece material is improved. Therefore, how to safely and reliably recycle waste lithium iron phosphate with low energy consumption and environmental protection and solve the source and cost problems of the ultra-pure ferric phosphate of the raw material of the lithium iron phosphate pole piece material is the key to solve the problems. However, at present, a process for purifying the high-recovery and reuse value product of the ultrapure ferric phosphate by using the waste lithium iron phosphate pole piece material as a raw material is not successfully adopted, so that development of a comprehensive recovery and reuse technology for solving the waste lithium iron phosphate pole piece material resources is urgently needed.
Disclosure of Invention
In order to achieve the above purpose, the invention provides a method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials and the obtained ultrapure ferric phosphate, wherein the process of preparing the ultrapure ferric phosphate from waste lithium iron phosphate by utilizing a flow battery does not damage the pole piece structure, does not generate any waste matters, prepares and obtains the ultrapure ferric phosphate, can be used as a precursor for preparing the lithium iron phosphate again, realizes sustainable recycling of the waste lithium iron phosphate in a circulating way, has high recycling benefit, and solves the problems existing in the prior art.
The technical scheme adopted by the invention is that the method for obtaining the ultrapure ferric phosphate from the waste lithium iron phosphate pole piece material is characterized by comprising the following steps:
s1, obtaining a waste lithium iron phosphate pole piece material;
s2, washing, alcohol washing and drying the obtained waste lithium iron phosphate pole piece material to obtain a pretreated waste lithium iron phosphate pole piece material, and filling the pretreated waste lithium iron phosphate pole piece material into a mesh bag for later use;
s3, constructing a flow battery, wherein the flow battery comprises a battery unit, a positive and negative circulating pump and a positive and negative electrolyte storage tank; positive electrolyte and negative electrolyte are respectively stored in the positive electrolyte storage tank and the negative electrolyte storage tank; the positive electrode electrolyte adopts a redox couple with the potential higher than or equal to that of lithium iron phosphate as an active substance; when the flow battery is a symmetrical flow battery, the negative electrode electrolyte adopts the same active substance as the positive electrode electrolyte; when the flow battery is a flow battery full battery, the negative electrode electrolyte adopts potassium sulfide, zinc bromide, zinc chloride and ZnBr 2 Any one of the methyl viologen is used as an active material of the negative electrode electrolyte;
s4, preparing ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials: when the flow battery is a symmetrical flow battery, the positive and negative electrolyte liquid storage tanks are both provided with mesh bags filled with waste lithium iron phosphate pole piece materials; then constant current charge and discharge are carried out on the flow battery, and in the charge and discharge cycle process of the flow battery, active substances in the positive and negative electrolyte respectively carry out targeted lithium removal reaction on the waste lithium iron phosphate pole piece materials in the positive and negative electrolyte liquid storage tanks;
when the flow battery is a full-flow battery, only the positive electrolyte liquid storage tank is provided with a mesh bag filled with waste lithium iron phosphate pole piece materials, then constant current charge and discharge are carried out on the flow battery, and in the process of charge and discharge circulation of the flow battery, active substances in the positive electrolyte perform targeted lithium removal reaction on the waste lithium iron phosphate pole piece materials in the positive electrolyte liquid storage tank;
and taking out the waste lithium iron phosphate pole piece material after undergoing a charge-discharge cycle, and washing and drying to obtain the ultrapure ferric phosphate.
Further, in S2, the drying process specifically includes: and drying the waste lithium iron phosphate pole piece material subjected to water washing and alcohol washing at 50-100 ℃ for 1-48 h.
Further, in S3, the battery unit includes a positive electrode, a separator, and a negative electrode; the top end of the positive electrode is provided with a positive electrode liquid outlet, the positive electrode liquid outlet is connected with a liquid inlet at the top end of a positive electrode liquid storage tank through a transmission pipeline, the liquid outlet at the bottom end of the positive electrode electrolyte liquid storage tank is connected with a positive electrode circulating pump through the transmission pipeline, and the positive electrode circulating pump is connected with the liquid inlet at the bottom end of the positive electrode through the transmission pipeline;
the top end of the negative electrode is provided with a negative electrode liquid outlet, the negative electrode liquid outlet is connected with a liquid inlet at the top end of a negative electrode electrolyte liquid storage tank through a transmission pipeline, the liquid outlet at the bottom end of the negative electrode electrolyte liquid storage tank is connected with a negative electrode circulating pump through the transmission pipeline, and the negative electrode circulating pump is connected with the liquid inlet at the bottom end of the negative electrode through the transmission pipeline;
the membrane comprises any one of Nafion membrane, PE membrane, PP membrane, SPEEK membrane, PBI membrane, PEO membrane, SPES membrane, PIFA membrane, PVDF membrane and modified membrane of each membrane.
Further, in S3, the concentration of the supporting electrolyte of the positive electrode electrolyte is 0.1 mol/L-2 mol/L, and the supporting electrolyte comprises any one or more of potassium chloride, sodium chloride, lithium chloride, ammonium chloride, lithium carbonate, sulfuric acid, hydrochloric acid, potassium hydroxide, sodium hydroxide and lithium hydroxide;
the concentration of the supporting electrolyte of the negative electrode electrolyte is 0.1 mol/L-5 mol/L, and the supporting electrolyte comprises any one or more of potassium chloride, sodium chloride, lithium chloride, ammonium chloride, lithium carbonate, sulfuric acid, hydrochloric acid, potassium hydroxide, sodium hydroxide and lithium hydroxide.
Further, the negative electrode electrolyte uses the same supporting electrolyte as the positive electrode electrolyte.
Further, in S3, the concentration of the active material adopted in the positive electrode electrolyte is 0.01mol/L to 3mol/L; the concentration of the active material adopted in the negative electrode electrolyte is 0.1 mol/L-6 mol/L.
Further, the active material used in the positive electrode electrolyte includes: ferrocene and derivative thereof, tetramethyl piperidine oxide derivative, thiazole derivative, thiazine derivative and C 13 H 11 NO、WCl 4 N 3 S 2 、C 33 H 29 N 2 S 2 P 2 Pt、C 6 H 4 S 4 、[Fe(CN) 6 ] 3- /[Fe(CN) 6 ] 4- Couple of electricity, VO 2+ /VO 2 + Couple, fe 2+ /Fe 3+ Pair of electric poles, I - /I 3- Couple, br - /Br 2 Pair of electricity, mn 3+ /Mn 2+ Pair of electricity, ce 4+ /Ce 3+ Couple of electricity, co 3 /Co 2+ Pair of electricity, ce 2 O 6- /Ce 3+ Any one of the electrical pairs.
Further, ferrocene and derivatives thereof are selected from any one of ammonium ferrocene sulfonate, monochloroferrocene, dibromoferrocene and methanolic ferrocene;
tetramethyl piperidine oxide derivatives using C 10 H 18 NO 3 、(C 13 H 22 O 3 N) n 、C 16 H 22 NO 3 、C 10 H 20 NO 4 Any one of S;
thiazole derivatives, C 6 Cl 2 N 2 S 4 、C 13 H 11 S 2 N、C 20 H 14 S 2 N 2 O、C 14 H 13 S 2 NO、C 4 Cl 2 N 2 S 4 、C 6 S 4 N 2 、C 10 H 4 N 2 S 4 、C 8 F 5 S 2 ClN、C 6 H 4 S 2 N、C 6 H 8 N 4 S、C 4 H 5 N 5 S 3 、C 10 H 6 N 2 S、C 3 H 6 N 3 S 2 、CHN 2 S 2 And derivatives, C thereof 10 H 6 N 2 Any one of S;
CHN 2 S 2 and derivatives thereof, using: CHN (CHN) 2 S 2 、C 8 H 7 N 2 S 2 、C 8 H 7 N 2 S 2 O、C 7 H 5 N 2 S 2 、C 7 H 4 N 2 S 2 Cl、C 3 H 6 N 3 S 2 Any one of them;
thiazine derivatives are prepared from the following steps: phenothiazine, chlorophenothiazine, methylphenothiazine, acetylphenothiazine, C 2 N 3 Cl 2 S、C 11 H 10 BrNS 2 、C 11 H 11 NS 2 、C 6 H 9 NS 5 、C 12 H 13 NOS 2 、S 3 N 3 O 2 、C 6 H 7 NS 5 Any one of them;
[Fe(CN) 6 ] 3- /[Fe(CN) 6 ] 4- the pair adopts any one of potassium ferricyanide, ammonium ferrocyanide, potassium ferrocyanide and sodium ferrocyanide;
VO 2+ /VO 2 + a pair of electrodes adopts vanadyl sulfate;
Fe 2+ /Fe 3+ the pair adopts any one of ferric chloride, ferrous chloride, ferric sulfate and ferrous sulfate;
I - /I 3- a pair of electrodes adopts potassium iodide or sodium iodide;
Br - /Br 2 a pair of electrodes adopts potassium bromide or sodium bromide;
Mn 3+ /Mn 2+ a pair of electrodes adopts manganese chloride or manganese trichloride;
Ce 4+ /Ce 3+ a pair of electrodes adopts cerium chloride or cerium sulfate;
Ce 2 O 6+ /Ce 3+ cerium perchlorate or cerium oxyperchlorate is used.
Further, CHN 2 S 2 And derivatives thereof, including CHN 2 S 2 、C 8 H 7 N 2 S 2 、C 8 H 7 N 2 S 2 O、C 7 H 5 N 2 S 2 、C 7 H 4 N 2 S 2 Cl、C 3 H 6 N 3 S 2 Any one of them.
The ultra-pure ferric phosphate is obtained by the method for obtaining the ultra-pure ferric phosphate from the waste lithium iron phosphate pole piece material.
The beneficial effects of the invention are as follows:
(1) The method adopts the flow battery to recycle the waste lithium iron phosphate pole piece material, thereby preparing and obtaining the ultra-high purity ferric phosphate, the flow battery is utilized to prepare the ultra-high purity ferric phosphate from the waste lithium iron phosphate, the pole piece structure is not damaged, no waste is generated, the ultra-high purity ferric phosphate is prepared and obtained, the ultra-high purity ferric phosphate can be used as a precursor for preparing the lithium iron phosphate again, the recycling process is safe and reliable, the operation is simple, the environment is friendly, and due to the ultra-high cycling stability of the flow battery, the recycling sustainable recycling of the waste lithium iron phosphate can be realized, the recycling benefit is high, the large-scale production and commercial production of the process for preparing the ultra-high purity ferric phosphate from the waste lithium iron phosphate by the propulsion flow battery are facilitated, and the problems of mass retirement of the waste lithium iron phosphate battery in the future are hopefully realized.
(2) According to the invention, the redox targeted reaction flow battery based on high reaction rate is adopted to perform targeted treatment on the waste lithium iron phosphate pole piece material stored in the liquid storage tank, the advantages of high safety, environmental friendliness, power and energy separation and the like of the flow battery are brought into play, the high-content state of oxidation state active substances is maintained in the charging/discharging process of the flow battery, the rapid targeted oxidation of the waste lithium iron phosphate can be realized, and the ultra-pure ferric phosphate is obtained.
(3) The high cycle performance of the flow battery can realize the recovery treatment of a plurality of batches of waste lithium iron phosphate; the characteristic of energy and power separation creates the theoretical infinite amplification of the electrolyte liquid storage tank, can realize the recovery treatment of a large amount of waste lithium iron phosphate, and is easy to realize scale; compared with dry recovery and wet recovery of multiple chemical substances, the flow battery of the application is used for recovering and preparing ultrapure ferric phosphate by waste lithium iron phosphate pole piece materials in a simple chemical environment at normal temperature, and the recovery process is safe and reliable.
(4) According to the invention, by adopting two schemes of a flow battery full battery and a symmetrical battery, the combination of the preparation of the ultrapure ferric phosphate from the waste lithium iron phosphate and the energy storage field can be realized, and meanwhile, the symmetrical flow battery can realize the preparation of the ultrapure ferric phosphate from the waste lithium iron phosphate with ultralow energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an embodiment of the present invention for producing ultrapure ferric phosphate from spent lithium iron phosphate using a flow battery.
FIG. 2 is a cyclic voltammogram of a flow battery employing ferrocene ammonium sulfonate as the positive electrolyte active material in accordance with an embodiment of the present invention.
FIG. 3 is a solid XRD pattern of waste lithium iron phosphate charged and recovered by a flow battery using ferrocene ammonium sulfonate as the active material of the positive electrolyte in the embodiment of the invention.
Fig. 4 is a solid XRD pattern of the waste lithium iron phosphate according to the embodiment of the present invention after being recovered by charging a flow battery using potassium ferricyanide as the positive electrode active material.
Fig. 5 is a solid XRD pattern of the waste lithium iron phosphate according to the embodiment of the present invention after the waste lithium iron phosphate is recovered by charging a flow battery using ferric chloride as the positive active material.
Fig. 6 is a voltage plot of charge capacity before and after adding waste lithium iron phosphate pole piece materials into a symmetrical flow battery using ferrocene ammonium sulfonate as positive and negative active materials in an embodiment of the invention.
FIG. 7 is a solid XRD pattern of waste lithium iron phosphate recovered by charging a flow battery using ferrocene ammonium sulfonate as the positive and negative active material in an embodiment of the invention.
FIG. 8 is a long cycle chart of the multiple recovery of waste lithium iron phosphate pole piece materials of the flow battery adopting ferrocene ammonium sulfonate as the positive electrolyte active material in the embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method for obtaining the ultrapure ferric phosphate from the waste lithium iron phosphate pole piece material comprises the following steps:
s1, obtaining a waste lithium iron phosphate pole piece material;
the source of the waste lithium iron phosphate pole piece material is waste lithium ion battery anode material.
S2, washing the obtained waste lithium iron phosphate pole piece material with water and alcohol, drying the washed waste lithium iron phosphate pole piece material at 50-100 ℃ for 1-48 h to obtain a pretreated waste lithium iron phosphate pole piece material, and filling the pretreated waste lithium iron phosphate pole piece material into a mesh bag for later use.
S3, constructing a flow battery, wherein the flow battery comprises a battery unit, a positive and negative circulating pump and a positive and negative electrolyte storage tank as shown in FIG 1; the battery unit comprises a positive electrode, a diaphragm and a negative electrode; the top end of the positive electrode is provided with a positive electrode liquid outlet, the positive electrode liquid outlet is connected with a liquid inlet at the top end of the positive electrode liquid storage tank through a transmission pipeline, the liquid outlet at the bottom end of the positive electrode electrolyte liquid storage tank is connected with a positive electrode circulating pump through a transmission pipeline, and the positive electrode circulating pump is connected with the liquid inlet at the bottom end of the positive electrode through the transmission pipeline; the top of negative pole is provided with the negative pole liquid outlet, and the liquid inlet on negative pole liquid storage pot top is connected through transmission line to the negative pole liquid outlet, and the liquid outlet on negative pole liquid storage pot bottom is connected through transmission line to the negative pole circulating pump, and the negative pole circulating pump passes through the liquid inlet on transmission line connection negative pole bottom.
The supporting electrolyte of the positive electrode electrolyte comprises any one or more of potassium chloride, sodium chloride, lithium chloride, ammonium chloride, lithium carbonate, sulfuric acid, hydrochloric acid, potassium hydroxide, sodium hydroxide and lithium hydroxide. The concentration of the supporting electrolyte of the positive electrode electrolyte is 0.1 mol/L-2 mol/L.
The supporting electrolyte of the negative electrode electrolyte comprises any one or more of potassium chloride, sodium chloride, lithium chloride, ammonium chloride, lithium carbonate, sulfuric acid, hydrochloric acid, potassium hydroxide, sodium hydroxide and lithium hydroxide. The concentration range of the negative electrode electrolyte supporting electrolyte is 0.1 mol/L-5 mol/L.
To maintain the ionic balance of the positive and negative electrolytes, the positive and negative electrolytes preferably use the same supporting electrolyte.
The concentration of the positive and negative electrode electrolyte is 0.01M to the limit concentration of active substances;
the positive electrode electrolyte adopts a redox couple with the potential higher than or equal to that of lithium iron phosphate as an active material; when the flow battery is a symmetrical flow battery, the negative electrode electrolyte adopts the same active substance as the positive electrode electrolyte, the positive electrode and the negative electrode both recover the waste lithium iron phosphate pole piece material to prepare ultrapure ferric phosphate, and at the moment, the waste lithium iron phosphate pole piece material is placed in the positive electrode electrolyte liquid storage tanks, so that the treatment capacity and the treatment speed of purifying the ferric phosphate by the waste lithium iron phosphate pole piece are greatly improved; when the flow battery is a flow battery full battery, the negative electrode electrolyte adopts any one of potassium sulfide, zinc bromide and zinc chloride as an active substance of the negative electrode electrolyte, only the positive electrode recovers and prepares ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials, and only the positive electrode electrolyte liquid storage tank is used for placing the waste lithium iron phosphate pole piece materials.
The concentration of the positive electrode electrolyte active material is 0.01mol/L to 3mol/L.
The concentration of the negative electrode electrolyte active material is 0.1mol/L to 6mol/L.
Wherein the redox couple with the potential higher than or equal to that of the lithium iron phosphate is used as an active substance, and comprises an organic active substance and an inorganic active substance.
Wherein, organic active material scale cost is lower, and easily adjusts the nature, includes: ferrocene and derivative thereof, tetramethyl piperidine oxide derivative, thiazole derivative, thiazine derivative and C 13 H 11 NO (10-methyl benzoxazine)WCl 4 N 3 S 2 (amino thio-diimidazole tetrachloro-tungstic acid tetraphenylarsine)>C 33 H 29 N 2 S 2 P 2 Pt (P, P '-bis (diphenylphosphino) ethane- (Z) -S, S' -azabenzoylimine platinum disulfide)C 18 H 34 B 18 Ni (benzene (methyl dihalide two-carbon) nickel complex)>C 6 H 4 S 4 (tetrathiafulvalene) in->Any one of them.
The ferrocene and the derivative thereof are preferably any one of ammonium ferrocene sulfonate, monochloroferrocene, dibromoferrocene and methanolic ferrocene.
Tetramethyl piperidine oxide derivatives, preferably C 10 H 18 NO 3 (4-carboxy-2, 6-tetramethylpiperidine nitroxide), (C) 13 H 22 O 3 N) n (Poly (2, 6-tetramethylpiperidinazoxy-4-methacrylate)), C 16 H 22 NO 3 (2, 6-tetramethyl piperidine nitroxide radical-4-benzoate), C 10 H 20 NO 4 S (4-methylsulfonyloxy-2, 6-tetramethylpiperidine nitroxide radical)).
Thiazole derivatives: preferably C is used 6 Cl 2 N 2 S 4 、C 13 H 11 S 2 N、C 20 H 14 S 2 N 2 O、C 14 H 13 S 2 NO、C 4 Cl 2 N 2 S 4 、C 6 S 4 N 2 、C 10 H 4 N 2 S 4 、C 8 F 5 S 2 ClN、C 6 H 4 S 2 N、C 6 H 8 N 4 S、C 4 H 5 N 5 S 3 、C 10 H 6 N 2 S、C 3 H 6 N 3 S 2 、CHN 2 S 2 And derivatives, C thereof 10 H 6 N 2 S.
Wherein C is 6 Cl 2 N 2 S 4 4, 8-Dichlorobenzo [1,2-d:4,5-d ]']Bis ([ 1,2, 3)]Dithiazole), the structural formula is:
C 13 H 11 S 2 n, 5-methyl-2-phenyl-1, 3, 2-benzodithiazole, the structural formula is:
C 20 H 14 S 2 N 2 o,2- [4- (1, 3-benzoxazole)-2-yl) phenyl]-5-methyl-1, 3, 2-benzodithiazole of the formula:
C 14 H 13 S 2 NO,2- (4-methoxyphenyl) -5-methyl-1, 3, 2-benzodithiazole, having the structural formula:
C 4 Cl 2 N 2 S 4 4,4' -dichloro-3λ 2 ,3’λ 2 -5,5' -bis (1, 2, 3-dithiazole) of the formula:
C 6 S 4 N 2 ，2λ 2 ,6λ 2 benzo [1,2-d:4,5-d ]']Bis ([ 1,3, 2)]Dithiazole), the structural formula is:
C 10 H 4 N 2 S 4 naphthalene [2,1-d:6,5-d ]']Bis ([ 1,2, 3)]Dithiazole), the structural formula is:
C 8 F 5 S 2 ClN, 4-chloro-5- (perfluorophenyl) -1,2, 3-dithiazole substituent of the formula:
C 6 H 4 S 2 n, benzo [ d ]][1,3,2]Dithiazole hexafluorophosphate having the structural formula:
C 6 H 8 N 4 s,4, 7-dimethyl-4, 7-dihydro- [1,2,5]Thiadiazolo [3,4-b ]]Pyrazine, structural formula is:
C 4 H 5 N 5 S 3 ，[1,2,3]dithiazolo [4,5-b ]][1,2,5]Thiadiazolo [3,4-e ]]Pyrazine substituents of the formula:
C 10 H 6 N 2 s, naphtho [1,2-c ]][1,2,5]Thiadiazole of the structural formula:
C 3 H 6 N 3 S 2 n, N-dimethyl-3H-1, 2,3, 5-dithiadiazole-4-amine;
CHN 2 S 2 3H-1,2,3, 5-dithiadiazole-3-radical) and derivatives thereof;
C 10 H 6 N 2 s,1H, 3H-naphthalene [1,8-cd ]][1,2,6]Thiadiazine of the formula:
CHN 2 S 2 (3H-1, 2,3, 5-dithiadiazole-3-radical) and its derivatives are preferably employed:
CHN 2 S 2 (3H-1, 2,3, 5-dithiadiazole)
C 8 H 7 N 2 S 2 (4- (p-tolyl) -3H-1,2,3, 5-dithiadiazole)
C 8 H 7 N 2 S 2 O (4- (4-methoxyphenyl) -3H-1,2,3, 5-dithiadiazole)
C 7 H 5 N 2 S 2 (4-phenyl-3H-1, 2,3, 5-dithiadiazole)
C 7 H 4 N 2 S 2 Cl (4- (4-chlorophenyl) -3H-1,2,3, 5-dithiadiazole)
C 3 H 6 N 3 S 2 (N, N-dimethyl-3H-1, 2,3, 5-dithiadiazole-4-amine)Any one of them. The thiazine derivative is preferably selected from:
phenothiazines
Chlorphenothiazine
Methyl phenothiazine
Acetyl phenothiazines
C 2 N 3 Cl 2 S (3, 5-dichloro-1, 2,4, 6-thiatriazinyl)
C 11 H 10 BrNS 2 (3- (4-bromophenyl) -5, 6-dimethyl-1, 4, 2-dithiazide)
C 11 H 11 NS 2 (5, 6-dimethyl-3-phenyl-1, 4, 2-dithiazide)
C 6 H 9 NS 5 (3, 5, 6-tris (methylsulfanyl) -1,4, 2-dithiazide)
C 12 H 13 NOS 2 (3- (4-methoxyphenyl) -5, 6-dimethyl-1, 4, 2-dithiazide)
S 3 N 3 O 2 (1, 1-dihydroxy-1 lambda) 4 ,3,5,2,4λ 2 ,6λ 2 -triazatriazines-2-tritium
C 6 H 7 NS 5 (6, 7-dihydro-3- (methylthio) - [1,4 ]]Dithio [2,3-e]-1,4, 2-dithiazide
Any one of them.
Inorganic active materials are readily available, including: [ Fe (CN) 6 ] 3- /[Fe(CN) 6 ] 4- Couple of electricity, VO 2+ /VO 2 + Couple, fe 2 + /Fe 3+ Pair of electric poles, I - /I 3- Couple, br - /Br 2 Pair of electricity, mn 3+ /Mn 2+ Pair of electricity, ce 4+ /Ce 3+ Couple of electricity, co 3 /Co 2+ Pair of electricity, ce 2 O 6- /Ce 3 + Any one of the electrical pairs.
[Fe(CN) 6 ] 3- /[Fe(CN) 6 ] 4- For the pair, any one of potassium ferricyanide, ammonium ferrocyanide, potassium ferrocyanide, sodium ferrocyanide and sodium ferricyanide is preferably used.
VO 2+ /VO 2 + For the pair, vanadyl sulfate is preferably used.
Fe 2+ /Fe 3+ For the pair, any of ferric chloride, ferrous chloride, ferric sulfate and ferrous sulfate is preferably used.
I - /I 3- For the pair, potassium iodide or sodium iodide is preferably used.
Br - /Br 2 For the pair, potassium bromide or sodium bromide is preferably used.
Mn 3+ /Mn 2+ Manganese chloride or manganese trichloride is preferably used for the pair.
Ce 4+ /Ce 3+ For the pair, cerium chloride or cerium sulfate is preferably used.
Ce 2 O 6+ /Ce 3+ Cerium perchlorate or cerium oxyperchlorate is preferably used.
The membrane comprises any one of Nafion membrane, PE membrane, PP membrane, SPEEK membrane, PBI membrane, PEO membrane, SPES membrane, PIFA membrane, PVDF membrane and modified membrane of each membrane.
S4, preparing ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials: when the flow battery is a symmetrical flow battery, the positive and negative electrolyte liquid storage tanks are both provided with mesh bags filled with waste lithium iron phosphate pole piece materials; then constant current charge and discharge is carried out on the flow battery, and the current density is set to be 0.5 mA.cm -2 ～300mA·cm -2 In the charge-discharge cycle process of the flow battery, based on redox targeted reaction, active substances higher than or equal to lithium iron phosphate potential in the positive and negative electrolyte respectively perform targeted lithium removal reaction on waste lithium iron phosphate pole piece materials in a positive and negative electrolyte liquid storage tank;
when the flow battery is a flow battery full battery, only the positive electrolyte liquid storage tank is provided with a mesh bag filled with waste lithium iron phosphate pole piece materials, and then constant current charge and discharge is carried out on the flow battery, wherein the current density is set to be 0.5 mA.cm -2 ～300mA·cm -2 In the charge-discharge cycle process of the flow battery, based on the oxidation-reduction targeted reaction, active substances higher than or equal to the potential of lithium iron phosphate in the positive electrode electrolyte perform targeted lithium removal reaction on the waste lithium iron phosphate pole piece materials in the positive electrode electrolyte liquid storage tank;
after the waste lithium iron phosphate pole piece material is subjected to a charge-discharge cycle, the ultra-high purity lithium iron phosphate precursor ferric phosphate which keeps the integral structure of the pole piece material is obtained after washing and drying, so that the ultra-high purity ferric phosphate is safely, reliably, simply and efficiently prepared from the waste lithium iron phosphate pole piece material.
The waste lithium iron phosphate pole piece material can be placed in an electrolyte liquid storage tank under any charge state of the flow battery, the preferable placement time is more than 50% of SOC/SOD, and the extraction time is after the waste lithium iron phosphate pole piece material is subjected to a partial or complete charging or discharging process.
Through XRD result test, after a discharge/charge process, the waste lithium iron phosphate is completely converted into ultrapure ferric phosphate, which is mainly beneficial to the fact that high-potential or equipotential active substances can keep high SOC/SOD under the charge/discharge effect of a flow battery, so that the waste lithium iron phosphate is subjected to high-speed targeted oxidation.
The reaction principle of the step S4 is specifically as follows:
for active substances with potential higher than that of the waste lithium iron phosphate pole piece material, the high potential has an oxidation effect on the low potential, lithium iron phosphate can be removed, and the high-potential active substances can be kept in a high-concentration state in the charge and discharge process of the flow battery, so that high-speed targeted oxidation of lithium iron phosphate is kept;
as for the active substance with the same potential as that of the waste lithium iron phosphate pole piece material, according to the Nernst equation, with the progress of the charge and discharge process, the Nernst potential of the active substance is gradually higher than that of the lithium iron phosphate, so that the target oxidation of the lithium iron phosphate is realized, and the ultra-pure ferric phosphate is prepared.
The lithium iron phosphate pole piece material is purified into a lithium iron phosphate material, and the removed lithium element enters electrolyte, so that the flow battery adopted by the application is a conductive cation flow battery, and the lithium element exists in a solution in a cation form, has no influence on the circularity of the flow battery until the service life of the flow battery is exhausted, and is recovered along with waste liquid.
Taking potassium ferricyanide-potassium sulfide flow battery as an example:
the reaction occurring at the positive electrode is:
the reaction occurring at the negative electrode is:
the targeted reaction of the active substance and lithium iron phosphate is as follows:
the invention will be further described with reference to examples and figures.
Example 1
The method for obtaining the ultrapure ferric phosphate from the waste lithium iron phosphate pole piece material comprises the following steps:
s1, obtaining a waste lithium iron phosphate pole piece material;
s2, washing, alcohol washing and drying the obtained waste lithium iron phosphate pole piece material to obtain a pretreated waste lithium iron phosphate pole piece material, and filling the pretreated waste lithium iron phosphate pole piece material into a mesh bag for later use;
s3, constructing a flow battery, wherein the flow battery comprises a battery unit, a positive and negative circulating pump and a positive and negative electrolyte liquid storage tank; the positive and negative electrolyte storage tanks are respectively stored with positive electrolyte and negative electrolyte;
the supporting electrolyte in the positive electrolyte is 0.5M sodium chloride+0.5M ammonium chloride;
the active material in the positive electrode electrolyte adopts ferrocene ammonium sulfonate with the concentration of 10mM;
the supporting electrolyte in the negative electrode electrolyte is 0.5M sodium chloride+0.5M ammonium chloride;
ZnBr with active material of 1M in negative electrode electrolyte 2 +zinc foil mounted and fixed inside the battery;
the preparation process of ferrocene ammonium sulfonate comprises the following steps: 5g of ferrocene is weighed and dissolved in 60mL of acetic anhydride, 3g of chlorosulfonic acid is dropwise added into the solution under the condition of room temperature, the solution is stirred, the temperature is controlled to be 30 ℃, the solution is kept stand until the reaction is completed, then the solution is placed in an ice-water bath, 40mL of absolute ethyl alcohol is slowly added, the solution is naturally cooled to room temperature, the solvent is removed under reduced pressure, the residue is dissolved in the absolute ethyl alcohol, 50mL of ammonia methanol solution is dropwise added into the mixed solution, and after the solid is completely separated out, the yellow brown solid, namely ferrocene ammonium sulfonate, is obtained through suction filtration.
The working electrode is a glassy carbon electrode, the counter electrode is a platinum electrode, the reference electrode is a silver/silver chloride electrode, the sweeping speed is set to be 100mV/s, the voltage is set to be 0V and 0.8V, and the cyclic voltammetry test is carried out on ferrocene ammonium sulfonate. The data are shown in figure 2, with ammonium ferrocenesulfonate exhibiting excellent reversibility.
S4, preparing ultrapure ferric phosphate from the waste lithium iron phosphate pole piece material, wherein the positive electrode electrolyte liquid storage tank is a reaction place for recycling the waste lithium iron phosphate pole piece material, a filter is arranged in the positive electrode electrolyte liquid storage tank to bear the waste lithium iron phosphate pole piece material, a net bag filled with the waste lithium iron phosphate pole piece material is placed in the positive electrode electrolyte liquid storage tank of the flow battery in a charging initial state of the flow battery, constant current cyclic charge and discharge testing is carried out on the flow battery, the waste lithium iron phosphate pole piece material is taken out by draining the solution after one charge and discharge cycle, deionized water and absolute ethyl alcohol are used for cleaning treatment in sequence, and after drying, the ultrapure ferric phosphate is obtained.
The above experiment was repeated at intervals during the flow battery charge and discharge cycle.
The XRD pattern of the product of this example, as shown in FIG. 3, shows that the spent lithium iron phosphate pole piece material has been fully converted to ferric phosphate, yielding ultrapure ferric phosphate. The flow battery cycle efficiency graph of fig. 8 shows that the flow battery does not suffer from cycle performance degradation due to the addition of spent lithium iron phosphate. Therefore, the same flow battery can be utilized to recycle a large amount of waste lithium iron phosphate pole piece materials for multiple times. Lays a foundation for the large-scale commercialization of the process for preparing the ultrapure ferric phosphate by recycling the waste lithium iron phosphate by the flow battery.
Example 2
In the embodiment, the method is suitable for preparing ultrapure ferric phosphate from waste lithium iron phosphate by an iron-sulfur flow battery:
in addition to the step S3 of the method,
the supporting electrolyte in the positive electrode electrolyte is KCl, and the concentration of the supporting electrolyte is 0.5M;
the active material in the positive electrolyte adopts potassium ferricyanide K 3 Fe(CN) 6 Concentration is 0.6M;
the supporting electrolyte in the negative electrode electrolyte is KCl, and the concentration is 0.5M;
the active material in the negative electrode electrolyte is K 2 S, the concentration is 2M;
the remainder was the same as in example 1.
The XRD pattern of the product of this example, as shown in FIG. 4, shows that the spent lithium iron phosphate pole piece material has been fully converted to ferric phosphate, yielding ultrapure ferric phosphate.
Example 3
In the embodiment, the method is suitable for preparing ultrapure ferric phosphate from waste lithium iron phosphate by a zinc-iron flow battery:
in addition to the step S3 of the method,
the supporting electrolyte in the positive electrolyte is KOH, and the concentration of the KOH is 1M;
the active material in the positive electrode electrolyte adopts ferric chloride FeCl 2 Concentration is 0.3M;
the supporting electrolyte in the negative electrode electrolyte is KOH, and the concentration is 1M;
the active material in the negative electrode electrolyte is ZnBr 2 Concentration is 0.5M;
the remainder was the same as in example 1.
The XRD pattern of the product of this example, as shown in FIG. 5, shows that the waste lithium iron phosphate pole piece material has been fully converted to ferric phosphate, resulting in ultrapure ferric phosphate, and the preparation of ultrapure ferric phosphate from waste lithium iron phosphate is achieved.
Example 4
In the embodiment, the method is suitable for preparing the ultra-pure ferric phosphate from the waste lithium iron phosphate by the ultra-low energy consumption symmetrical flow battery:
in addition to the step S3 of the method,
the supporting electrolyte in the positive electrolyte is NH 4 Cl at a concentration of 0.5M;
the active material in the positive electrode electrolyte adopts ferrocene ammonium sulfonate with the concentration of 0.6M;
the supporting electrolyte in the negative electrode electrolyte is NH 4 Cl concentration was 0.5M;
the active material in the negative electrode electrolyte is ferrocene ammonium sulfonate, and the concentration is 0.6M;
s4, the positive and negative electrolyte liquid storage tanks are reaction places for recycling waste lithium iron phosphate pole piece materials, filters are arranged in the positive and negative electrolyte liquid storage tanks to bear the waste lithium iron phosphate pole piece materials, the symmetrical flow battery is in a charging initial state, mesh bags containing the waste lithium iron phosphate pole piece materials are respectively arranged in the positive and negative electrolyte liquid storage tanks of the flow battery, constant current cyclic charge and discharge testing is conducted on the symmetrical flow battery, after one charge and discharge cycle, draining solution is conducted, the waste lithium iron phosphate pole piece materials are taken out, deionized water and absolute ethyl alcohol are used for cleaning treatment in sequence, and ultra-pure ferric phosphate is obtained after drying.
The remainder was the same as in example 1.
The capacity voltage diagram of the symmetrical battery of the flow battery shown in fig. 6 shows that the symmetrical flow battery has low energy consumption for recycling the waste lithium iron phosphate, and ultra-pure ferric phosphate is recycled and prepared from the waste lithium iron phosphate at ultra-low cost. LFP in fig. 6 refers to lithium iron phosphate LiFePO 4 . The XRD pattern of FIG. 7 shows that the waste lithium iron phosphate has been completely converted into ferric phosphate, so that the ultra-pure ferric phosphate is obtained, and the preparation of the ultra-pure ferric phosphate from the waste lithium iron phosphate is realized.
Other examples except for S3, the positive and negative electrolyte solvents, supporting electrolytes, and active materials are shown in table 1, and the following specific examples are as follows:
TABLE 1 supporting electrolyte and active materials in Positive and negative electrolytes in the remaining examples
/>
It should be noted that in this application relational terms such as first, second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (3)
1. The method for obtaining the ultrapure ferric phosphate from the waste lithium iron phosphate pole piece material is characterized by comprising the following steps of:
s1, obtaining a waste lithium iron phosphate pole piece material;
s2, washing, alcohol washing and drying the obtained waste lithium iron phosphate pole piece material to obtain a pretreated waste lithium iron phosphate pole piece material, and filling the pretreated waste lithium iron phosphate pole piece material into a mesh bag for later use;
s3, constructing a flow battery, wherein the flow battery comprises a battery unit, a positive and negative circulating pump and a positive and negative electrolyte storage tank; positive electrolyte and negative electrolyte are respectively stored in the positive electrolyte storage tank and the negative electrolyte storage tank; the positive electrode electrolyte adopts a redox couple with the potential higher than or equal to that of lithium iron phosphate as an active substance;
the flow battery is a symmetrical flow battery, the negative electrolyte adopts the same active substance as the positive electrolyte, and the negative electrolyte adopts the same supporting electrolyte as the positive electrolyte;
the concentration of the supporting electrolyte of the positive electrode electrolyte and the negative electrode electrolyte is 0.1 mol/L-2 mol/L, and the supporting electrolyte is any one or more of potassium chloride, sodium chloride, ammonium chloride, lithium carbonate, sulfuric acid, hydrochloric acid, potassium hydroxide, sodium hydroxide and lithium hydroxide;
the active material used in the positive electrode electrolyte is selected from: ferrocene ammonium sulfonate, monochloroferrocene, methanolic ferrocene, tetramethylpiperidine oxide derivative, thiazole derivative, thiazine derivative, 10-methylbenzoxazine, aminothiodiimidazole tetraphenylarsine tetrachlorophthalic acid, P' -bis (diphenylphosphino) ethane-Z) -any one of S, S' -azabenzoylimine platinum disulfide;
the derivative of the tetramethylpiperidine oxide is a derivative of tetramethylpiperidine oxide, adopts 4-carboxyl-2, 6-tetramethyl piperidine nitroxide, poly (2, 6-tetramethyl piperidine nitroxide-4-methyl acrylate) any one of 2, 6-tetramethyl piperidine nitroxide radical-4-benzoate and 4-methylsulfonyloxy-2, 6-tetramethyl piperidine nitroxide radical;
the thiazole derivative adopts 4, 8-dichlorobenzo [1,2-d:4,5-d ]']Bis ([ 1,2, 3)]Dithiazoles), 5-methyl-2-phenyl-1, 3, 2-benzodithiazoles, 2- [4- (1, 3-benzooxazol-2-yl) phenyl]-5-methyl-1, 3, 2-benzodithiazole, 2- (4-methoxyphenyl) -5-methyl-1, 3, 2-benzodithiazole, 4' -dichloro-3λ 2 ,3’λ 2 -5,5' -bis (1, 2, 3-dithiazole), 2λ 2 ,6λ 2 Benzo [1,2-d:4,5-d ]']Bis ([ 1,3, 2)]Dithiazole), naphthalene [2,1-d:6,5-d ]']Bis ([ 1,2, 3)]Dithiazole), benzo [d][1,3,2]Dithiazole hexafluorophosphate, 4, 7-dimethyl-4, 7-dihydro- [1,2,5]Thiadiazolo [3,4-b ]]Pyrazines, naphtho [1,2-c][1,2,5]Thiadiazole, 3H-1,2,3, 5-dithiadiazole, 4- (p-tolyl) -3H-1,2,3, 5-dithiadiazole, 4- (4-methoxyphenyl) -3H-1,2,3, 5-dithiadiazole, 4-phenyl-3H-1, 2,3, 5-dithiadiazole, 4- (4-chlorophenyl) -3H-1,2,3, 5-dithiadiazole, N-dimethyl-3H-1, 2,3, 5-dithiadiazole-4-amine, 1H, 3H-naphthalene [1,8-cd][1,2,6]Any one of thiadiazine;
the thiazine derivative adopts the following steps: phenothiazine, chlorophenothiazine and methylphenolThiazine, acetylphenothiazine, 3- (4-bromophenyl) -5, 6-dimethyl-1, 4, 2-dithiazine, 5, 6-dimethyl-3-phenyl-1, 4, 2-dithiazine, 3,5, 6-tris (methylsulfanyl) -1,4, 2-dithiazine, 3- (4-methoxyphenyl) -5, 6-dimethyl-1, 4, 2-dithiazine, 1-dihydroxy-1λ 4 ,3,5,2,4λ 2 ,6λ 2 -triazatriazine-2-tritium, 6, 7-dihydro-3- (methylthio) - [1,4]Dithio [2,3-e]-any one of 1,4, 2-dithiazide;
the concentration of active substances adopted in the positive electrode electrolyte is 0.01 mol/L-3 mol/L;
the concentration of active substances adopted in the negative electrode electrolyte is 0.1 mol/L-6 mol/L;
s4, preparing ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials: the positive and negative electrolyte storage tanks are respectively provided with a mesh bag filled with waste lithium iron phosphate pole piece materials; then constant current charge and discharge are carried out on the flow battery, and in the charge and discharge cycle process of the flow battery, active substances in the positive and negative electrolyte respectively carry out targeted lithium removal reaction on the waste lithium iron phosphate pole piece materials in the positive and negative electrolyte liquid storage tanks;
taking out the waste lithium iron phosphate pole piece material after undergoing a charge-discharge cycle, and washing and drying to obtain the ultrapure ferric phosphate;
the placing time of the waste lithium iron phosphate pole piece material is SOC/SOD >50%.
2. The method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece materials according to claim 1, wherein in S2, the drying treatment is specifically: and drying the waste lithium iron phosphate pole piece material subjected to water washing and alcohol washing at the temperature of 50-100 ℃ for 1-48 h.
3. The method for obtaining ultrapure ferric phosphate from a waste lithium iron phosphate pole piece material according to claim 1, wherein in S3, the battery unit comprises a positive electrode, a diaphragm and a negative electrode; the top end of the positive electrode is provided with a positive electrode liquid outlet, the positive electrode liquid outlet is connected with a liquid inlet at the top end of a positive electrode liquid storage tank through a transmission pipeline, the liquid outlet at the bottom end of the positive electrode electrolyte liquid storage tank is connected with a positive electrode circulating pump through the transmission pipeline, and the positive electrode circulating pump is connected with the liquid inlet at the bottom end of the positive electrode through the transmission pipeline;
the top end of the negative electrode is provided with a negative electrode liquid outlet, the negative electrode liquid outlet is connected with a liquid inlet at the top end of a negative electrode electrolyte liquid storage tank through a transmission pipeline, the liquid outlet at the bottom end of the negative electrode electrolyte liquid storage tank is connected with a negative electrode circulating pump through the transmission pipeline, and the negative electrode circulating pump is connected with the liquid inlet at the bottom end of the negative electrode through the transmission pipeline;
the membrane is selected from any one of Nafion membrane, PE membrane, PP membrane, SPEEK membrane, PBI membrane, PEO membrane, SPES membrane and PVDF membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252423.9A CN114084877B (en) | 2021-10-26 | 2021-10-26 | Method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece material and obtained ultrapure ferric phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111252423.9A CN114084877B (en) | 2021-10-26 | 2021-10-26 | Method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece material and obtained ultrapure ferric phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114084877A CN114084877A (en) | 2022-02-25 |
| CN114084877B true CN114084877B (en) | 2024-01-16 |
Family
ID=80297955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111252423.9A Active CN114084877B (en) | 2021-10-26 | 2021-10-26 | Method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece material and obtained ultrapure ferric phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114084877B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115161658B (en) * | 2022-06-29 | 2024-05-28 | 电子科技大学 | Preparation method and application of olivine-type ferric phosphate material |
| CN115432681B (en) * | 2022-08-08 | 2023-08-15 | 广西博世科环保科技股份有限公司 | Regeneration process of waste lithium iron phosphate battery anode material |
| CN115744943A (en) * | 2022-11-29 | 2023-03-07 | 长沙道尚循环科技有限公司 | Method for recycling lithium iron phosphate battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600340A (en) * | 2014-12-26 | 2015-05-06 | 上海电气集团股份有限公司 | Electrode frame structure of single batteries in redox flow battery as well as single battery and electric pile |
| CN105206856A (en) * | 2015-07-29 | 2015-12-30 | 上海电气集团股份有限公司 | Novel lithium ion flow cell |
| WO2020235121A1 (en) * | 2019-05-20 | 2020-11-26 | パナソニックＩｐマネジメント株式会社 | Flow battery |
| CN113258114A (en) * | 2021-04-20 | 2021-08-13 | 哈尔滨工业大学 | Stable and high-capacity neutral aqueous liquid flow lithium battery based on redox targeting reaction |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3799178A4 (en) * | 2018-05-21 | 2021-08-18 | Panasonic Intellectual Property Management Co., Ltd. | Flow battery |
| US11271238B2 (en) * | 2018-11-27 | 2022-03-08 | Utah State University | Applications of low-cost, thermal and electrochemically stable organic compounds as high performance redox active materials in redox flow batteries |
-
2021
- 2021-10-26 CN CN202111252423.9A patent/CN114084877B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600340A (en) * | 2014-12-26 | 2015-05-06 | 上海电气集团股份有限公司 | Electrode frame structure of single batteries in redox flow battery as well as single battery and electric pile |
| CN105206856A (en) * | 2015-07-29 | 2015-12-30 | 上海电气集团股份有限公司 | Novel lithium ion flow cell |
| WO2020235121A1 (en) * | 2019-05-20 | 2020-11-26 | パナソニックＩｐマネジメント株式会社 | Flow battery |
| CN113258114A (en) * | 2021-04-20 | 2021-08-13 | 哈尔滨工业大学 | Stable and high-capacity neutral aqueous liquid flow lithium battery based on redox targeting reaction |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
Non-Patent Citations (2)
| Title |
|---|
| "A redox targeting-based material recycling strategy for spent lithium ion batteries";Juezhi Yu等，;《Energy&Environmental Science》;20190802;第2672-2677页 * |
| 氧化还原靶向原理在液流电池中的应用进展;蔡兴华 等;化学工业与工程;第73-79页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114084877A (en) | 2022-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114084877B (en) | Method for obtaining ultrapure ferric phosphate from waste lithium iron phosphate pole piece material and obtained ultrapure ferric phosphate | |
| DeBruler et al. | Designer two-electron storage viologen anolyte materials for neutral aqueous organic redox flow batteries | |
| CN103000924B (en) | Organic phase dual flow battery | |
| US20130266836A1 (en) | Hybrid Energy Storage Systems Utilizing Redox Active Organic Compounds | |
| CN109599577B (en) | Water phase system organic flow battery system based on salt cavern | |
| CN102354762B (en) | A kind of preparation method of high-purity vanadium battery electrolyte | |
| CN105990617A (en) | Method for recycling and regenerating waste lithium ion battery electrode materials | |
| US20210391605A1 (en) | A lithium ion battery materials recycling method | |
| CN110668996B (en) | Bipyridine compound, synthetic method and symmetrical flow battery system thereof | |
| US20220073448A1 (en) | Method for synthesizing carboxy-containing anthraquinone derivative, carboxy-containing anthraquinone derivative prepared thereby, and battery system comprising same | |
| CN109802118A (en) | A kind of preparation method of the rechargeable magnesium battery based on two selenizing vanadium anodes | |
| CN103545524B (en) | Zinc-Polyaniline Cell and preparation method thereof | |
| CN110867587A (en) | Neutral water system mixed liquid flow battery with high power and long service life based on pyridylphenoxazine | |
| CN105826543A (en) | Aluminum-polyaniline secondary battery | |
| CN102244285A (en) | High-concentration zinc-vanadium redox battery | |
| CN107154487A (en) | A kind of utilization organic dyestuff discarded object makes the method and its application that novel energy stores material | |
| CN114497547A (en) | Conjugated quinozine organic electrode material and preparation method and application thereof | |
| CN109461948A (en) | Utilize the method for the electrolyte liquid regeneration V electrolyte of failure vanadium cell | |
| CN106784756B (en) | A kind of preparation method of the composite material for anode | |
| Xu et al. | Novel organic redox flow batteries using soluble quinonoid compounds as positive materials | |
| WO2023091087A2 (en) | A recycling method for active materials in lithium or sodium batteries | |
| CN102376970B (en) | Method for preparing all-vanadium ion redox flow battery electrolyte | |
| CN104300167A (en) | Organic phase flow battery | |
| CN109148910A (en) | Utilize the method for the electrolyte liquid regeneration V electrolyte of failure vanadium cell | |
| CN113299937B (en) | Method for recycling waste zinc-manganese dry batteries and directly using waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |